复合赤铁矿和铜矿石载氧体在化学链燃烧中的循环反应性能研究

doi:10.12096/j.2096-4528.pgt.22086

发电技术 ›› 2022, Vol. 43 ›› Issue (4): 574-583.DOI: 10.12096/j.2096-4528.pgt.22086

• 碳捕集、利用与封存技术 • 上一篇下一篇

复合赤铁矿和铜矿石载氧体在化学链燃烧中的循环反应性能研究

苗桢武¹, 沈来宏¹(), 赵海波²

^1.东南大学能源与环境学院, 江苏省南京市 210096
^2.煤燃烧国家重点实验室(华中科技大学), 湖北省武汉市 430074

收稿日期:2022-04-25 出版日期:2022-08-31 发布日期:2022-09-06
作者简介:苗桢武(1997)，男，博士研究生，主要研究方向为化学链技术，miaozw@seu.edu.cn；
沈来宏(1965)，男，博士，教授，主要研究方向为化学链技术、洁净煤燃烧技术、生物质气化制氢、气体火焰稳燃等，本文通信作者，Lhshen@seu.edu.cn；
沈来宏(1965)，男，博士，教授，主要研究方向为化学链技术、洁净煤燃烧技术、生物质气化制氢、气体火焰稳燃等，本文通信作者，Lhshen@seu.edu.cn；
赵海波(1977)，男，博士，教授，主要研究方向为湍流气固两相流的建模和数值模拟、离散系统动力学的随机算法、电厂专家分析平台、化学链燃烧和环境热经济，hzhao@mail.hust.edu.cn。
基金资助:
国家自然科学基金项目(520746044)

Study on Cycling Reaction Performance of Composite Hematite and Copper Ore Oxygen Carrier in Chemical Looping Combustion

Zhenwu MIAO¹, Laihong SHEN¹(), Haibo ZHAO²

^1.School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu Province, China
^2.State Key Laboratory of Coal Combustion (Huazhong University of Science and Technology), Wuhan 430074, Hubei Province, China

Received:2022-04-25 Published:2022-08-31 Online:2022-09-06
Supported by:
National Natural Science Foundation of China(520746044)

摘要/Abstract

摘要：

单一天然矿石载氧体(oxygen carrier，OC)由于存在反应活性差且循环稳定性低的问题，限制了其在工业上的应用。针对喷雾干燥造粒法制备的复合赤铁矿和铜矿石OC，在流化床热重分析仪(fluidized bed thermogravimetric analyzer，FB-TGA)上对其进行了长期化学链燃烧(chemical looping combustion，CLC)循环测试。结果表明：新鲜OC颗粒表面存在部分富集的细微颗粒，较大的机械应力导致OC在流化初期磨损率较高，流化6 min后颗粒磨损率稳定在0.28%/h。在氧化还原循环反应过程中，OC受到化学应力和热应力的作用，机械强度降低，颗粒磨损和烧结加剧。此外，颗粒烧结抑制了氧化阶段的进行，导致OC被深度还原至更低价态，从而促进了颗粒团聚并最终完全失流。因此，降低载氧率和在燃料反应器中的停留时间有利于OC在工业上的安全运行。

关键词: CO₂捕集, 化学链燃烧, 循环反应性能, 喷雾干燥造粒, 载氧体, 团聚

Abstract:

The low reactivity and low cycle stability of single natural oxygen carrier (OC) limit its application in industry. Composite OC of hematite and copper ore was prepared by spray drying granulating method, and the chemical looping combustion (CLC) cycle test was performed on the fluidized bed thermogravimetric analyzer (FB-TGA). The results show that the attrition rate of OC is relatively high at the initial stage of fluidization due to the presence of some enriched fine particles on the surface of fresh OC particles, and the particle attrition rate is stable at 0.28%/h after 6 min of fluidization. In the process of redox cycle reaction, the mechanical strength of OC is reduced by chemical stress and thermal stress, and the particle attrition and sintering are intensified. In addition, the particle sintering inhibits the oxidation stage, leading to the deep reduction of OC to a lower state, which promotes particle agglomeration and eventual defluidization. Therefore, the reduction of oxygen carrier rate and residence time in fuel reactor is beneficial to the safe operation of OC in industry.

Key words: CO₂capture, chemical looping combustion, cycling reaction performance, spray drying granulation, oxygen carrier (OC), agglomeration

中图分类号:

TK 16

苗桢武, 沈来宏, 赵海波. 复合赤铁矿和铜矿石载氧体在化学链燃烧中的循环反应性能研究[J]. 发电技术, 2022, 43(4): 574-583.

Zhenwu MIAO, Laihong SHEN, Haibo ZHAO. Study on Cycling Reaction Performance of Composite Hematite and Copper Ore Oxygen Carrier in Chemical Looping Combustion[J]. Power Generation Technology, 2022, 43(4): 574-583.

图/表 12

表1 铜矿石和赤铁矿的化学组成

Tab. 1 Chemical composition of copper ore and hematite

赤铁矿		铜矿
成分	质量分数/%	成分	质量分数/%
Fe₂O₃	90.65	Fe₂O₃	59.36
SiO₂	4.73	CuO	34.09
Al₂O₃	1.16	SiO₂	3.08
其他	3.46	Al₂O₃	1.02
		其他	2.45

图1 OC的XRD图谱

Fig. 1 XRD pattern of OC

图2 FB-TGA示意图

Fig. 2 Schematic diagram of FB-TGA

图3 在FB-TGA中OC的质量和磨损率随时间的变化曲线

Fig. 3 Variation curves of mass and attrition rates of OC with time in FB-TGA

图4 喷雾干燥造粒法制备的新鲜OC颗粒

Fig. 4 Fresh OC prepared by spray drying granulation

图5 900 ℃时FB-TGA中多次氧化还原循环中的质量和压降变化曲线

Fig. 5 Mass and pressure drop curves of multiple redox cycles in FB-TGA at 900 ℃

图6 每个循环中氧化还原反应的净失质量和质量变化

Fig. 6 Net mass loss and mass change of redox reaction in each cycle

图7 不同氧化还原循环次数时的反应速率

Fig. 7 Reaction rates at different redox cycles

图8 FB-TGA中温度的变化曲线

Fig. 8 Temperature variation curves in FB-TGA

图9 前、中、后期中5次循环床层温度的变化曲线

Fig. 9 Variation curves of bed temperature for five cycles in early, middle and late stages

图10 氧化还原循环后床层表面的OC颗粒图像

Fig. 10 Image of OC particles on the bed surface after redox cycles

图11 氧化还原循环后床层内部的OC颗粒图像

Fig. 11 Image of OC particles inside the bed after redox cycles

参考文献 20

1	姜红丽，刘羽茜，冯一铭，等．碳达峰、碳中和背景下“十四五”时期发电技术趋势分析[J]．发电技术，2022，43(1)：54-64． doi:10.12096/j.2096-4528.pgt.21030
	JIANG H L， LIU Y X， FENG Y M，et al ．Analysis of power generation technology trend in 14th five-year plan under the background of carbon peak and carbon neutrality[J]．Power Generation Technology，2022，43(1)：54-64． doi:10.12096/j.2096-4528.pgt.21030
2	邬炜，赵腾，李隽，等．考虑碳预算与碳循环的能源规划方法及建议[J]．电力建设，2021，42(10)：1-8． doi:10.12204/j.issn.1000-7229.2021.10.001
	WU W， ZHAO T， LI J，et al ．Energy planning methods and proposals considering carbon budget and carbon cycle[J]．Electric Power Construction，2021，42(10)：1-8． doi:10.12204/j.issn.1000-7229.2021.10.001
3	ADANEZ J， ABAD A， GARCIA L F，et al ．Progress in chemical-looping combustion and reforming technologies[J]．Progress in Energy and Combustion Science，2012，38(2)：215-282． doi:10.1016/j.pecs.2011.09.001
4	LIU L， LI Z， WANG Y，et al ．Industry-scale production of a perovskite oxide as oxygen carrier material in chemical looping[J]．Chemical Engineering Journal，2022，431：134006． doi:10.1016/j.cej.2021.134006
5	LIU L， LI Z， CAI N S ．Oxidization and reduction kinetics of a manganese oxygen carrier granulated with the spray drying method at a tonnage scale for chemical looping combustion[J]．Fuel，2021，303：121267． doi:10.1016/j.fuel.2021.121267
6	HOSSAIN M M， DE L H I ．Chemical-looping combustion (CLC) for inherent CO₂ separations：a review[J]．Chemical Engineering Science，2008，63(18)：4433-4451．
7	YANG W J， ZHAO H B， WANG K，et al ．Synergistic effects of mixtures of iron ores and copper ores as oxygen carriers in chemical-looping combustion[J]．Proceedings of the Combustion Institute，2015，35(3)：2811-2818． doi:10.1016/j.proci.2014.07.010
8	YANG W J， ZHAO H B， MA J C，et al ．Copper-decorated hematite as an oxygen carrier for in situ gasification chemical looping combustion of coal[J]．Energy & Fuels，2014，28(6)：3970-3981． doi:10.1021/ef5001584
9	LIU S Q， HE F， ZHAO K，et al ．Long-term coal chemical looping gasification using a bimetallic oxygen carrier of natural hematite and copper ore[J]．Fuel，2022，309：122106． doi:10.1016/j.fuel.2021.122106
10	JERNDAL E， MATTISSON T， THIJS I，et al ．NiO particles with Ca and Mg based additives produced by spray-drying as oxygen carriers for chemical-looping combustion[J]．Energy Procedia，2009，1(1)：479-486． doi:10.1016/j.egypro.2009.01.064
11	MATTISSON T， JERNDAL E， LINDERHOLM C，et al ．Reactivity of a spray-dried NiO/NiAl₂O₄ oxygen carrier for chemical-looping combustion[J]．Chemical Engineering Science，2011，66(20)：4636-4644． doi:10.1016/j.ces.2011.06.025
12	TIAN X， ZHAO H B， MA J C ．Cement bonded fine hematite and copper ore particles as oxygen carrier in chemical looping combustion[J]．Applied Energy，2017，204：242-253． doi:10.1016/j.apenergy.2017.07.025
13	SU Z， WANG Y N， DU H，et al ．Using copper ore and hematite fine particles as raw materials of an oxygen carrier for chemical cooping combustion of coal：spray drying granulation and performance evaluation[J]．Energy & Fuels，2020，34(7)：8587-8599． doi:10.1021/acs.energyfuels.0c01023
14	SIRIWARDANE R， RILEY J， BENINCOSA W，et al ．Development of CuFeMnAlO_4+δ oxygen carrier with high attrition resistance and 50-kW_th methane/air chemical looping combustion tests[J]．Applied Energy，2021，286：116507． doi:10.1016/j.apenergy.2021.116507
15	MENDIARA T， GARCÍA-LABIANO F， ABAD A，et al ．Air jet attrition measurements at hot conditions of oxygen carriers for chemical looping combustion[J]．Powder Technology，2021，392：661-671． doi:10.1016/j.powtec.2021.07.038
16	LIU F， KANG W L， SONG C，et al ．Crack propagation and attrition mechanism of oxygen carriers in chemical looping process[J]．Fuel，2022，310：122326． doi:10.1016/j.fuel.2021.122326
17	CABELLO A， GAYÁN P， ABAD A，et al ．Long-lasting Cu-based oxygen carrier material for industrial scale in chemical looping combustion[J]．International Journal of Greenhouse Gas Control，2016，52：120-129． doi:10.1016/j.ijggc.2016.06.023
18	张将，沈来宏，冯璇，等．CuFe₂O₄载氧体的释氧特性及其对煤化学链气化的影响[J]．燃烧科学与技术，2019，25(3)：220-228． doi:10.11715/rskxjs.R201901007
	ZHANG J， SHEN L H， FENG X，et al ．Oxygen release properties of CuFe₂O₄ oxygen carrier and its effect on chemical looping gasification of coal[J]．Journal of Combustion Science and Technology，2019，25(3)：220-228． doi:10.11715/rskxjs.R201901007
19	粟自然，沈来宏，闫景春，等．基于铁酸钙载氧体的稻壳化学链气化反应特性[J]．石油学报(石油加工)，2020，36(6)：1219-1228．
	LI Z R， SHEN L H， YAN J C，et al ．Characteristics of rice-hull chemical looping gasification with calcium-ferrite as oxygen carrier[J]．Acta Petrolei Sinica (Petroleum Processing Section)，2020，36(6)：1219-1228．
20	ZEVENHOVEN M， SEVONIUS C， SALMINEN P，et al ．Defluidization of the oxygen carrier ilmenite：laboratory experiments with potassium salts[J]．Energy，2018，148：930-940． doi:10.1016/j.energy.2018.01.184

[1]	李小端, 赵兴雷, 叶舣, 王保登, 熊日华. 基于电渗析技术的CO₂吸收剂再生过程研究[J]. 发电技术, 2022, 43(4): 593-599.
[2]	李振山, 陈虎, 李维成, 刘磊, 蔡宁生. 化学链燃烧中试系统的研究进展与展望[J]. 发电技术, 2022, 43(4): 544-561.

复合赤铁矿和铜矿石载氧体在化学链燃烧中的循环反应性能研究

Study on Cycling Reaction Performance of Composite Hematite and Copper Ore Oxygen Carrier in Chemical Looping Combustion

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 20

相关文章 2

编辑推荐

Metrics

本文评价